Self-assembling may be defined as the spontaneous association of material units into structures that are often capable of cyclic reorganization and functional behavior. Various molecular recognition processes stabilize assemblies of polymers and biological structures. The present article analyzes cases in which chemical, shape and other recognition mechanisms are individually or cooperatively operative. Simpler self-assembling theories reported in the literature are highlighted. Detailed processes for which chemical recognition is the prevailing, enthalpy-driven, process include the non-ideal component of miscibility, supramolecular polymerization, host-guest complexes and template polymerization. Also discussed are systems such as liquid crystalline closed polymers, ternary mesogenic systems and rigid crystalline polymers for which shape recognition is the prevailing entropy-driven process. Other recognition mechanisms include ion condensation effects, hydrophobic bonding and growth-coupled-to-orientation. Combinations of various recognition mechanisms are particularly evident in biological structures. Self-assembling mechanisms involved in the genesis of some biological systems can be scientifically identified, but much more needs to be known to describe the "engineered" assembling modes that support complex functional organs.
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http://dx.doi.org/10.1039/d0sm01301c | DOI Listing |
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